JP2019508355A - Carbonaceous material and method of using the same - Google Patents

Abstract

The present disclosure is a composition comprising at least two different carbonaceous components, wherein at least one is typically a surface-modified carbonaceous particulate material having a relatively high springback, The present invention relates to a composition wherein one other component is generally a carbonaceous particulate material (eg, graphite etc.) having lower springback and / or higher BET specific surface area than the surface modified carbonaceous material component. Such compositions are particularly useful for producing negative electrodes for lithium ion batteries and the like, due to their beneficial electrochemical properties, particularly their beneficial electrochemical properties in automotive and energy storage applications. The present disclosure also relates to the use of a low springback carbonaceous particulate material as an additive in a carbonaceous composition, said composition being compared to a cell having an anode without said carbonaceous additive. It is used to make an anode for a Li-ion battery to increase the electrode density, cell capacity and / or cycle stability of the Li-ion battery while maintaining the power density.

Description

  The present disclosure is a composition comprising at least two different carbonaceous components, wherein at least one is typically a surface-modified carbonaceous particulate material having a relatively high springback, The present invention relates to a composition wherein one other component is generally a carbonaceous particulate material (eg, graphite etc.) having lower springback and / or higher BET specific surface area than the surface modified carbonaceous material component. Such compositions are particularly useful for producing negative electrodes for lithium ion batteries and the like, due to their electrochemical properties, in particular their electrochemical properties in automotive and energy storage applications.

  The present disclosure also relates to the use of low springback carbonaceous particulate material as an additive in carbonaceous compositions. The composition, for example, to increase the electrode density, cell capacity and / or cycling stability of the battery, while maintaining the power density of the cell compared to the anode without the carbonaceous additive It is used to manufacture an anode for a battery.

  Lithium ion batteries have become the battery technology of choice for consumer electronics products such as laptop computers, smart phones, video cameras and digital still cameras. Compared to other battery chemistries, one of the advantages of lithium ion battery systems is the high energy density and specific energy combined with high power performance for average cell voltage of about 3.5 V and lightweight electrode material About. Over more than 20 years from the introduction of the first lithium ion battery by Sony in 1991, lithium ion cells have significantly improved in terms of energy density. This development has been motivated, inter alia, by the increase in energy consumption and the trend towards miniaturization of electronic devices that require reduced accumulator volume and increased electrochemical cell capacity.

  In recent years, lithium ion batteries have been used to buffer the peak consumption of power in electrical grids, for example when used in hybrid applications, plug-ins and full electric vehicles, for example when incorporated into electrical grids, and Energy storage systems have also been considered to integrate renewable energy generation such as variable wind power and solar energy generation.

  For automotive applications, the energy of cells per volume (cell capacity or energy density) and the energy of cells per mass (specific energy) are important for the improvement of the limited travel range, which is still the main obstacle of electric vehicles Play a role. At the same time, because of the significantly longer lifespan required by the automotive industry, power suppliers and end users of such batteries, the battery's charge rate, cycle stability and durability make it possible, in the case of such applications, to More important than the case.

  Because batteries used for energy storage applications are mostly stationary battery applications, cell volume and mass are not as important as other applications, such as mobile applications. On the other hand, cell durability at a predetermined capacity retention rate and the number of charge and discharge cycles are important parameters in such an application. This is compatible with ensuring the highest level of battery safety, an important prerequisite for the diffusion of lithium cell technology to any desired application.

  While it is desirable to improve in parallel all key cell parameters such as energy density, power density, durability and safety, improving one parameter often adversely affects other cell parameters. For example, energy density can typically not be increased without compromising power density, safety or durability, or vice versa. Thus, in cell design and engineering of Li-ion batteries, one of ordinary skill in the art must generally accept the trade-off between various cell parameters.

  One important component that affects the electrochemical properties of Li-ion cells is the negative electrode (anode). In some Li-ion batteries, the anode comprises a carbonaceous material, such as graphite, as the electrochemically active material. Such a carbon material participates in the electrochemical redox process generated at the electrode by intercalating and de-intercalating lithium in the charge and discharge process, so that the characteristic of the carbonaceous material is It is expected to play an important role in battery performance characteristics. In the art, it is widely accepted that graphite anodes are limited in terms of charge acceptance and are the main cause of limitations on charge rate, which is an important requirement especially for lithium ion batteries for automobiles There is.

  For these reasons, a variety of different carbonaceous materials, such as graphite, have been developed in the art. For example, WO 2013/149807 of Imerys Graphite & Carbon, either an oxidation treatment or a chemical vapor deposition (CVD) coating, provides a graphite material with improved surface properties Describes a method for surface modification of graphite particles obtained by Although both methods are fundamentally different from one another and produce separate graphite particles, both methods result in graphite particles having advantageous properties over unmodified graphite itself. The co-pending PCT application (PCT / EP2015 / 066212), which is also published as Imeris Graphite & Carbon WO 2016/008951 (A1), comprises a surface-modified carbonaceous material, For example, graphite and the like are disclosed, and unmodified natural or synthetic carbon precursors are first applied to an amorphous carbon coating (e.g. CVD) and then the coated material is exposed to an oxygen containing atmosphere. This procedure results in surface-modified carbonaceous particles that are more hydrophilic than amorphous carbon-coated particles prior to surface oxidation ("activation").

  It was an object to provide a carbonaceous material useful as an active material for the negative electrode of a lithium ion battery. In particular, there is a continuing need in the art for carbonaceous materials having useful properties when used as an active material in lithium ion battery negative electrodes for automotive applications (such as electric vehicles) or energy storage applications. . Particularly in such applications, it is desirable to improve cycle performance and durability without simultaneously sacrificing cell capacity and cell output.

  Surprisingly, the present inventors combine at least two different carbonaceous materials (eg graphite etc.) into a composition of carbonaceous particles and use such a composition in an electrode, eg negative electrode, lithium It has been found to provide an electrode that can improve the cycling performance (eg cycle stability), durability, electrode resistance, current discharge characteristics, reversible capacity and / or safety of the ion battery.

  That is, in a first aspect, the present disclosure typically provides high spring-back, typically, for example, ≧ about 20% (ie, about 20% or more), or 約 about 30%, or 約 about 40%. And at least one surface-modified carbonaceous particulate material ("high-springback surface-modified carbonaceous particles") characterized by Back, eg, at least one carbonaceous particulate material (eg, graphite) “low springback carbonaceous particles” characterized by springback of ≦ about 18% (ie less than about 18%), or ≦ about 15% It relates to the composition containing. For example, the springback of the first surface modified (high springback) carbonaceous particulate material is about 20% to about 70%, such as about 20% to about 25%, about 25% to about 65%, About 30% to about 60%, about 35% to about 55%, about 40% to about 60%, about 45% to about 55%, about 50% to about 60%, about 55% to about 65%, or about It can be 55% to about 60%. Furthermore, for example, the springback of the second (low springback) carbonaceous particulate material is about 5% to about 15%, such as about 5% to about 7%, about 5% to about 10 %%, about 5% -About 12%, about 7% to about 12%, about 10% to about 15%, or about 12% to about 15%. In some embodiments, the first surface modified (high springback) carbonaceous particulate material is at least 2%, at least 5% greater than the springback of the second (low springback) carbonaceous particulate material , May have at least 10%, at least 15%, at least 20%, or at least 25% greater springback. For example, the springback difference between the first surface modified (high springback) carbonaceous particulate material and the second (low springback) carbonaceous particulate material is 2% to about 30%, It can be 5% to 25%, 10% to 20%, 10% to 25%, 5% to 15%, or 10% to 25%. Thus, for example, the first surface-modified (high springback) carbonaceous particulate material can have about 20% to about 70% springback and the second (low springback) carbonaceous The material can have about 5% to about 15% springback. As another example, the first surface-modified (high springback) carbonaceous particulate material can have about 40% to about 60% springback and a second (low springback) carbon The quality material can have a springback of about 10% to about 15%. In yet another example, the first surface-modified (high springback) carbonaceous particulate material can have about 55% to about 65% springback and the second (low springback) The carbonaceous material can have a springback of about 5% to about 12%. Other combinations in accordance with the above discussion are similarly contemplated and are included herein. Typically, the BET SSA of the low springback carbonaceous particulate material is higher than the BET SSA of the surface modified carbonaceous material.

In some embodiments, the high springback surface modified carbonaceous particles are by a core of natural or synthetic graphite modified by a chemical process and / or less than about 20 m ² / g, eg 4 .1m characterized by ² / ^g~20m relatively low BET specific surface area is ² / g (BET SSA). In some embodiments, for example, the surface of carbonaceous (eg, natural or synthetic graphite) particles may be oxidized and / or subjected to processes that affect the crystallinity of the surface. Such processes include, but are not limited to, the processes shown in WO 2013/149807 or PCT / EP2015 / 066212, respectively. Surface modified carbonaceous particles of high spring back is less than about ^{20 m} 2 / g, less than about ^{15 m} 2 / g, less than about ^{10 m} 2 / g, or relatively low BET ratio of less than about 6-8 m ² / g It is characterized by surface area (BET SSA). If necessary, their BET SSA ^is the 4.1m ² / g~20m 2 / g, or 4.5m ² / g~15m ² / g, or 4.1m ² / g~10m ² / g be able to. The low springback carbonaceous particulate material, which can typically be present in amounts up to 30% by weight (wt%), is, for example, about 5, 6, 7, 8 or 10 m ² / g in these embodiments. It is characterized as a highly crystalline unmodified graphite material with BET SSA generally higher than BET SSA of surface modified high springback graphite with BET SSA greater than.

  As shown in the Examples section below, such a combination of at least two different carbonaceous materials improves cycle performance and durability / safety without adversely affecting cell capacity and cell output of lithium ion batteries It can be used to advantage and is particularly useful in automotive and energy storage applications.

  Thus, another related aspect of the present disclosure is the use of a composition as defined herein for making a negative electrode of a Li-ion battery.

  As noted above, such electrodes, and corresponding Li-ion batteries, are particularly useful in automotive or energy storage applications such as, for example, electric vehicles, hybrid electric vehicles, or energy storage cells. Thus, a further aspect of the present disclosure relates to an electrode, a lithium ion battery, or an electric car, a hybrid electric car, or an energy comprising as an active material a composition as described herein as an active material in the anode of a Li ion battery Includes storage cells.

  Herein as a carbonaceous additive that increases cell capacity and / or cycle stability of a Li-ion battery while maintaining the power density of the cell as compared to a cell having the anode without the carbonaceous additive The use of a low springback carbonaceous material as defined represents another aspect of the present disclosure.

  Further, as defined herein as a carbonaceous additive that increases the density of the anode of a Li-ion battery while maintaining the power density of the cell as compared to a cell having the anode without the carbonaceous additive. The use of the low springback carbonaceous particulate material of the present invention is yet another aspect of the present disclosure.

  The present inventors have found that by carefully selecting at least two different carbonaceous components, it is possible to obtain a carbonaceous composition having good properties when used as an active material in a lithium ion battery negative electrode The

  Thus, in one aspect, the present disclosure provides at least one surface modified carbonaceous particulate material and at least one other carbonaceous material having lower springback than the surface modified carbonaceous particulate material. Provided is a composition comprising particulate material ("low springback carbonaceous material"). Typically, the BET SSA of the at least one low springback carbonaceous material is higher than the BET SSA of the at least one surface modified carbonaceous particulate material. The term "surface modified" in connection with graphite or carbonaceous particles, for example by introducing additional functional groups on the surface of the carbonaceous particles, or amorphous or at least essentially not on the surface of the carbonaceous particles It is generally understood to refer to particles whose surface is chemically modified by the addition of a layer of crystalline carbon, which may be complete or incomplete. Introducing additional functional groups, for example, exposes the carbonaceous particles to oxygen (or chemical species capable of releasing oxygen) under controlled conditions (altering the chemical composition of the surface of the particles) In contrast to simply exposing the particles, which may or may not be sufficient, to the air). The addition of amorphous / non-graphitic carbon is typically accomplished by pitch coating, plasma polymerization or various deposition techniques such as CVD. In other words, the term "surface modified" as used herein refers to other non-chemical means such as milling, grinding or abrasion (ie particles) In order not to reduce the size of the particles significantly, but to modify the shape of the particles, it does not include surface modifications caused only by mechanical manipulation of the particles, such as "grinding" the particles without grinding them.

  In some embodiments, the first surface modified carbonaceous particulate material has a springback of 約 about 20%, or 約 about 30%, or 約 about 40%. In such embodiments, this component is referred to as "high springback surface modified carbonaceous particulate material" (or particles). The term "about" as used herein is meant to be approximately the same as the referenced amount or value, and should be understood to include ± 5% of the specified amount or value.

In certain embodiments, the first (typically high springback) surface modified carbonaceous particulate material is less than 20 m ² / g, or less than 15 m ² / g, or 1 to 10 m ² / g, Or it can be characterized by BET SSA of 1 to 8 m ² / g, or 1 to 6 m ² / g. In some embodiments, the BET SSA of the surface modified carbonaceous particulate material may be higher than 4.0 m ² / g, for example at least 4.1, 4.2, 4.3, 4 It can be .4 or 4.5 m ² / g. Thus, in certain embodiments, the surface modified carbonaceous particulate material has a BET SSA of at least 4.1, 4.2, 4.3, 4.4 or 4.5 m ² / g or more and 20 m. less than ² / g, or ^15m less than 2 / g, or may be ^10m less than 2 / g.

The surface modified carbonaceous particulate material, in some embodiments, can be further characterized by several additional parameters, alone or in any possible combination:
a) Crystallite size L _{c of} 50 to 400 nm, or 60 to 200 nm, or 80 to 180 nm, or 100 to 150 nm (as measured by X-ray diffractometry (XRD));
b) 5 to 100 nm, 5 to 60 nm, or 6~40nm crystallite size _{L a} (as measured by Raman spectroscopy);
c) L _c / L _a ratio greater than 1.0, 1.5, 2.0, 2.5 or 3.0;
d) c / 2 distance of about 0.3353 to 0.3370 nm, or about 0.3354 to 0.3365 nm;
e) an oxygen content of more than 50 ppm, or more than 90 ppm, or more than 110 ppm;
f) Fe content of less than 20 ppm, or less than 10 ppm, or less than 5 ppm; and / or g) ash content of less than 0.04%, or less than 0.01%, or less than 0.005%.

In some embodiments, the at least one surface modified carbonaceous particulate material, alone or in any combination, can be further characterized by one or more of the following parameters:
h) pH value in aqueous suspension, which is about 5.0 to about 7.0, or 5.0 to 6.5, or 5.2 to 6, or 5.3 to 5.5;
i) a xylene density of about 2.24 to 2.26 g / cm ³ , or about 2.245 to 2.255 g / cm ³ , or about 2.25 to 2.255 g / cm ³ ; and / or j) 632. when measured with a laser having an excitation wavelength of 8 nm, less than about 0.3, or less than about 0.25, or less than about 0.2, or _I D / _{I G} ratio of less than about 0.15 (R (ID / IG)) (see the Method section below for more details on the determination of this parameter).
In such embodiments, the surface-modified carbonaceous material can be obtained, for example, by exposing the carbonaceous material, such as natural or synthetic graphite, to an oxygen-containing atmosphere for a predetermined time.

Suitable methods are, for example, described in more detail in WO 2013/149807, which is hereby incorporated by reference in its entirety. For example, in 2 to 30 minutes processing time at a temperature of 500 to 1100 ° C., the oxidation of synthetic graphite having a BET surface area of ^{1 m} 2 / g to about ^{15 m} 2 / g is in the composition of the claimed Surface-modified graphite can be produced which can be used as one component. It will be appreciated that certain adaptations (eg, length of exposure to oxygen-containing gas, choice of feedstock, etc.) are necessary to obtain materials exhibiting the desired parameters outlined above.

In another embodiment, at least one surface-modified carbonaceous particulate material in the composition is characterized by comprising non-graphitic, eg amorphous, carbonaceous coating coated with a carbon coating. it can. The at least one surface modified carbonaceous particulate material in these embodiments, alone or in combination, may be further characterized by any one of the following parameters:
k) a xylene density of 2.2 to 2.255 g / cm ³ , or 2.23 to 2.25 g / cm ³ ;
l) Crystallite size L _{c of} 80 to 350 nm or 100 to 160 nm;
m) Crystallite size L _a of 5 to 100 nm, or 20 to 60 nm;
n) an I _D / I _G ratio (R (I _D / I _G )) greater than about 0.3, or about 0.4 to 1.0, as measured by a laser having an excitation wavelength of 632.8 nm And / or o) an oxygen content of more than 80 ppm, or more than 200 ppm, or more than 300 ppm.

  In such embodiments, at least one surface modified carbonaceous particulate material coated with a non-graphitic material can be obtained, for example, by chemical vapor deposition (CVD) or similar techniques. Suitable methods that can be used in the context of the present disclosure and the resulting surface-modified carbonaceous particles are described in detail, for example, in WO 2013/149807 and WO 2013/149807. , The disclosure content of which is incorporated herein by reference in its entirety as previously described herein.

  For example, the amorphous carbon coating is typically mixed with an inert gas such as nitrogen or argon, for example in a rotary kiln or fluid bed, for a treatment time of typically 3 to 120 minutes, such as for example acetylene or propylene It is obtained by chemical vapor deposition of powdered natural or synthetic graphite raw materials at temperatures of 500-1200 ° C. using hydrocarbon gases. Again, certain adaptations to the process (eg, length of exposure to hydrocarbon gas, selection of hydrocarbon gas and feedstock, etc.) are required to obtain materials exhibiting the desired parameters outlined above. It will be understood that

  In yet another embodiment, the at least one surface modified carbonaceous particulate material is characterized by hydrophilic, non-graphitic, eg amorphous, carbon core particles with a carbon coating. Such hydrophilic non-graphite carbon coatings, for example, particles coated with carbonaceous core particles such as graphite, first with a layer of non-graphite, eg amorphous, carbon (eg by CVD) and then coated Can be obtained by exposure to an oxygen-containing gas atmosphere under controlled conditions, as described in PCT / EP2015 / 066212. The entire PCT / EP2015 / 066212 is incorporated herein by reference. Exposure to an oxygen containing atmosphere can increase the hydrophilicity of the carbonaceous particulate material, sometimes referred to herein as "activation" or "surface oxidation." Thus, the carbon coating of the hydrophilic surface-modified carbonaceous particulate material is, in one embodiment, comprised of oxidized amorphous carbon.

In some of these embodiments, the at least one hydrophilic surface-modified carbonaceous particulate material has increased wettability as compared to unoxidized (i.e., not activated) coated particles. Can be further characterized by Thus, the increased wettability can be expressed by measuring the contact angle of water droplets on the flat surface of the carbonaceous material. In these embodiments, the at least one hydrophilic surface-modified carbonaceous particulate material comprises
(I) a contact angle after 3 seconds which is less than 90 °, or less than 75 °, or less than 70 °, or less than 65 °; and / or
ii) a contact angle after 5 seconds of less than about 60 °, or less than 40 °, less than 30 °, less than 25 °, or less than 20 °; and / or (ii) at least 59 mJ / m ² or at least 62, 67 Or the surface energy of said hydrophilic surface modified carbonaceous particulate material of 70 mJ / m ² ;
It can be characterized by

In one embodiment, the at least one hydrophilic surface-modified carbonaceous particulate material in the composition comprises
(Iii) an oxygen content of more than about 200 ppm, more than about 400 ppm, more than about 600 ppm, more than about 700 ppm, or more than about 800 ppm; and / or (iv) less than 10.0 m ² / g, 8.0 m ² Mesopore area less than 0.5 g / g, less than 5.0 m ² / g, less than 4.0 m ² / g, less than 3.8 m ² / g, or less than 3.6 m ² / g;
Can be further characterized.

  Suitable methods and the resulting hydrophilic surface modified (coated) carbonaceous particles are described in detail, for example, in PCT / EP2015 / 066212, the disclosure content of which is incorporated herein by reference. It is incorporated herein by reference in its entirety as previously described in the specification.

In all of the above embodiments characterizing at least one surface-modified carbonaceous particulate material, the carbonaceous core of the particles is natural graphite, synthetic graphite, coke, exfoliated graphite, graphene, minority layer graphene (Few-layer graphene), graphite fiber, nanographite, non-graphite carbon, carbon black, petroleum or coal coke, glassy carbon, carbon nanotube, fullerene, carbon fiber, hard carbon, graphitized fine coke Or mixtures thereof, or further comprising particles of silicon, tin, bismuth, antimony, aluminum, silver, SiO _x (x = 0.2 to 1.8) or SnO _x (including SnO and SnO ₂ ) Charcoal It can be selected from the composition of the particles. In some embodiments, the core particles are natural or synthetic graphite particles, or a mixture of natural or synthetic graphite particles and silicon or other heteroatom particles.

  It is widely understood that particulate materials can be further characterized by their particle size and / or their particle size distribution (PSD). There are various ways to determine the PSD of particulate material (see the Methods section for some examples of PSD determination).

Thus, in some embodiments, the at least one surface modified carbonaceous particulate material has a D ₉₀ of 10 to 50 μm, or 15 to 45 μm, or 20 to 40 μm, and / or a D ₅₀ of It can be further characterized by a particle size distribution which is 5-40 μm, or 7-30 μm, or 10-25 μm.

The at least one surface modified carbonaceous particulate material in the composition can optionally be further characterized by one of the following parameters:
i) tap density of more than 0.7 g / cm ³ , or more than 0.8 g / cm ³ , or more than 0.9 g / cm ³ , or more than 0.95 g / cm ³ , or more than 1 g / cm ³ ;
ii) Fe content of less than 20 ppm, or less than 10 ppm, or less than 5 ppm; and / or
iii) Ash content less than 0.04%, or less than 0.01%, or less than 0.005%.

  As mentioned above, the composition of the present disclosure further comprises the first component, ie, at least one other carbonaceous material having lower springback as compared to the surface modified carbonaceous material. In some embodiments, the low springback carbonaceous particulate material can have a BET SSA that is higher than the BET SSA of the surface modified carbonaceous particulate material.

  Thus, the low springback carbonaceous particulate material can be characterized by ≦ about 18%, or ≦ about 16%, or ≦ about 15%, or ≦ about 12% springback in some embodiments.

Alternatively or additionally, the low springback carbonaceous particulate material further comprises ≧ about 5 m ² / g, or 約 about 6 m ² / g, or 約 about 7 m ² / g, or ≧ about 8 m ² / g, Or it can have a BET SSA of ≧ about 9 m ² / g, or ≧ about 10 m ² / g.

  The low springback carbonaceous particulate material as the second component of the composition is typically subjected to surface modification such as coating with non-graphitic carbon or surface oxidation (ie, chemical modification as described herein). It is not a carbonaceous material. On the other hand, in this context, the term unmodified means that in many embodiments the particles need to be ground or otherwise subjected to other mechanical forces, for example to obtain the desired particle size distribution. Because they allow pure mechanical manipulation of carbonaceous particles.

  In some embodiments, the low springback carbonaceous particulate material in the composition is natural or synthetic graphite, optionally high crystalline graphite.

As used herein, "high crystallinity" preferably refers to the interlayer distance c / 2, the actual density (xylene density), and / or the size of the crystalline domain in the particle (crystal size L _c ) It refers to the crystallinity of the characterized graphite particles. In such embodiments, the highly crystalline carbonaceous material has a c / 2 distance of ≦ 0.3370 nm, or ≦ 0.3365 nm, or ≦ 0.3362 nm, or ≦ 0.3360 nm and / or 2.230 g · It may be characterized by a xylene density greater than cm ⁻³ and / or L _{c of} at least 20 nm, or at least 40 nm, or at least 60 nm, or at least 80 nm, or at least 100 nm, or more.

The at least one low springback carbonaceous material is further characterized by any one of the following parameters, alone or in combination, as appropriate:
i) Particle size distribution in which D ₉₀ is 3 to 50 μm, or 5 to 30 μm, or 6 to 27 μm, or 10 to 20 μm;
ii) Particle size distribution, wherein D ₅₀ is 1 to 30 μm, or 2 to 20 μm, or 3 to 15 μm, or ₅ to 10 μm;
iii) Particle size distribution in which D ₁₀ is 0.5 to 10 μm, or 1 to 7 μm, or 1 to 5 μm, or 2 to 4 μm;
iv) Crystallite size L _c (as measured by XRD) of 30 to 400 nm, or 50 nm to 350 nm, or 70 nm to 250 nm;
v) Scott density less than about 0.4 g / cm ³ , or less than about 0.3 g / cm ³ , or less than about 0.25 g / cm ³ ;
vi) a xylene density of 2.24 to 2.27 g / cm ³ , or 2.25 to 2.265 g / cm ³ , or 2.255 to 2.265 g / cm ³ ; and / or
vii) an I _D / I _G ratio of less than about 0.3, or less than about 0.25, or less than about 0.2, or less than about 0.15, as measured by a laser having an excitation wavelength of 632.8 nm (R (I _D / I _G )).

In all of the above embodiments characterizing at least one low springback carbonaceous material, said material is natural graphite, synthetic graphite, coke, exfoliated graphite, graphene, few-layer graphene, graphite fiber, nanographite, graphitized fine coke Hard carbon, carbon black, petroleum-based or coal-based coke, non-graphite carbon including glassy carbon; carbon nanotube, fullerene, carbon fiber, mixture of any of these materials, or silicon, tin , bismuth, antimony, aluminum, _silver, it is selected from the composition of SiO X (X = 0.2~1.8) or _SnO x (including SnO and SnO ₂₎ according carbon particles comprising particles Kill. In some embodiments, the low springback carbonaceous particles are selected from natural or synthetic graphite particles, or a mixture of natural graphite particles and synthetic graphite particles.

As can be seen from the examples, the composition with the low springback component being synthetic or natural graphite with less than 15% springback, BET SSA of at least 8 m ² / g, c / 2 distance of ≦ 0.3358 nm is better Results were achieved. As further shown in the examples, the low springback component has a particle size distribution with a D ₉₀ diameter of 6 to 27 μm, a D ₅₀ diameter of 3 to 15 μm, and a D ₁₀ diameter of 1 to 5 μm. It can be synthetic or natural graphite.

  The at least one low springback carbonaceous particulate material is typically a minor component of the composition (i.e., less than 50% by weight of the composition), although it is not essential to be present as a minor component of the composition . In certain embodiments, the low springback graphite content is less than about 30%, or less than about 25%, or less than about 20%, or 1 to 25%, or 2 to 25% by weight of the composition. %, Or 2.5 to 20 mass%, or 2 to 18 mass%, or 2 to 15 mass%, or 2.5 to 15 mass%, or 5 to 15 mass%, or 10 to 15 mass%.

  As mentioned above, the first surface modified (high springback) carbonaceous particulate material is at least 5% higher than the springback of the second (low springback) carbonaceous particulate material, at least 5% It can have high, at least 10% high, at least 15% high, at least 20% high, or at least 25% high springback. For example, the springback difference between the first surface modified (high springback) carbonaceous particulate material and the second (low springback) carbonaceous particulate material is 2% to about 30%, It can be 5% to 25%, 10% to 20%, 10% to 25%, 5% to 15%, or 10% to 25%. In some embodiments, the springback of the first surface modified (high springback) carbonaceous particulate material is about 20% to about 70%, such as about 20% to about 25%, about 25% To about 65%, about 30% to about 60%, about 35% to about 55%, about 40% to about 60%, about 45% to about 55%, about 50% to about 60%, about 55% to about It can be 65%, or about 55% to about 60%. Furthermore, for example, the springback of the second (low springback) carbonaceous particulate material is about 5% to about 15%, such as about 5% to about 7%, about 5% to about 10 %%, about 5% -About 12%, about 7% to about 12%, about 10% to about 15%, or about 12% to about 15%. Thus, for example, the first surface-modified (high springback) carbonaceous particulate material can have about 20% to about 70% springback and the second (low springback) carbonaceous The material can have about 5% to about 15% springback. As another example, the first surface-modified (high springback) carbonaceous particulate material can have about 40% to about 60% springback and a second (low springback) carbon The quality material can have a springback of about 10% to about 15%. In yet another example, the first surface-modified (high springback) carbonaceous particulate material can have about 55% to about 65% springback and the second (low springback) The carbonaceous material can have a springback of about 5% to about 12% springback. Other combinations in accordance with the above discussion are similarly contemplated and are included herein.

  In addition to the two different carbonaceous particulate materials described in detail above, the composition may optionally further comprise at least one carbonaceous additive, said carbon optionally being The content of the quality additive is 0% by mass to 10% by mass, or 0.5% by mass to 5% by mass, or 1% by mass to 4% by mass. Preferred carbonaceous additives include natural graphite, synthetic graphite, coke, exfoliated graphite, graphene, few-layer graphene, graphite fiber, nanographite, graphitized fine coke; hard carbon, carbon black, petroleum-based or coal-based coke, Non-graphitized carbon containing glassy carbon; single-walled nanotubes (SWNT), carbon nanotubes including multiwalled nanotubes (MWNT); fullerenes, carbon fibers, or any of these materials Mixtures of, but not limited to, mixtures of For example, the composition comprises at least one surface-modified particulate carbonaceous material, at least one carbonaceous particulate material having a lower springback than at least one surface-modified particulate carbonaceous material (Eg, natural or synthetic graphite) and carbon black may be included.

The composition may optionally further include at least one non-carbonaceous component, and if necessary, the content of the non-carbonaceous component is more than 3% or more than 5%, Or more than 10%. Suitable non-carbonaceous additives include silicon, tin, bismuth, antimony, aluminum, silver, SiO _x (X = 0.2 to 1.8) or SnO _x (including SnO and SnO ₂ ) particles .

  Further, as the composition is particularly useful for making negative electrodes for Li-ion batteries, the composition may, in some embodiments, further comprise a polymeric binder material. Suitable polymeric binder materials are typically styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), carboxymethylcellulose (CMC), polyacrylic acid and derivatives thereof, polyfluorinated, in an amount of 1 to 5% by weight And vinylidene (PVDF) or mixtures thereof.

Use of a composition comprising at least one surface modified carbonaceous particulate material and at least one other carbonaceous particulate material The composition of the present disclosure is present as an active material in a negative electrode for a Li-ion battery In particular, the composition as defined herein, as it may have a beneficial combination of properties, is a negative electrode for a Li-ion battery, in particular a Li-ion battery-powered electric vehicle or a hybrid electric vehicle, or an energy storage unit Can be used to make a negative electrode for a Li-ion battery.

  While not intending to be bound by theory, the compositions disclosed herein (e.g., a first carbonaceous particulate material comprising a surface-modified carbonaceous particulate material and a non-surface-modified natural or synthetic material) Combining with a second carbonaceous particulate material comprising a carbonaceous material), when used in an electrode (e.g. the negative electrode of a Li-ion battery), promotes conductivity without interfering with the ability of the electrolyte to penetrate the electrode An improved particle-particle contact can be provided to ensure the necessary ionic conductivity at the electrode. For example, the second carbonaceous particulate material, together with the conductive surface-modified carbonaceous material, provides a three dimensional structure particularly suitable for electrochemical applications, with relatively low springback and / or compression characteristics. A highly conductive material can be included, for example, as a material for the anode of a Li-ion battery. As further noted above, the composition may include one or more additional high conductivity carbonaceous materials, and the one or more additional high conductivity carbonaceous materials may be chemically modified. Mention may be made, without limitation, of carbon black which may or may not be quality.

  Again, while not intending to be bound by theory, it is believed that the amount of secondary (low springback) carbonaceous material present can significantly affect battery performance. For example, by increasing the amount of the second (low springback) carbonaceous particulate material, the amount is generated by the three-dimensional structure (the assembly of the electrode material of the negative electrode, and thus the electrode of the liquid electrolyte) It is believed that the conductivity can be increased until it is high enough to fill the space within which prevents its ability to penetrate, which in particular limits the ionic conductivity which is essential for high current rate charging and discharging. As described above, the composition is less than 30% by mass, for example, 1% by mass to 25% by mass, 2.5 to 20% by mass, 2 to 15% by mass, 2.5 to 15% by mass, 5 to 15% by mass %, Or 10-15% by weight of the second (low springback) carbonaceous particulate material may be included. For example, the composition may comprise at least 50% by weight surface-modified carbonaceous particulate material (eg, 50% to 99% by weight, 70% to 98% by weight, 75% to 95% by weight, 85% by weight). % To 95% by weight, or 80% to 90% by weight of the surface-modified carbonaceous granular material), and 1% to 20% by mass of low springback carbonaceous granular material (for example, 2% by mass to 18%) %, 2% by mass to 15% by mass, 2.5% by mass to 15% by mass, 5% by mass to 15% by mass, or 10% by mass to 15% by mass of a low springback carbonaceous granular material). Such compositions can provide a suitable balance of cycle stability, electrode resistance, high current discharge characteristics and high reversible capacity when used at the anode of a Li-ion battery.

  Thus, another aspect of the present disclosure relates to at least one surface-modified carbonaceous particulate material having high springback, for example 20% or more, or 30% or more, or 40% or more. The use of a composition comprising low springback, for example at least one carbonaceous particulate material having lower springback, for example about 18% or less or about 15% or less, for manufacturing a lithium ion battery negative electrode . Such Li-ion batteries, in some embodiments, are adapted for use in electric vehicles, hybrid electric vehicles, or energy storage batteries.

  Typically, the use of the above composition to make the anode of a Li-ion battery may involve the composition as defined herein.

Downstream Products Using Surface-Modified Carbonaceous Particulate Material Accordingly, a lithium ion battery negative electrode comprising a composition as defined herein as an active material represents another aspect of the present disclosure. This aspect includes an electrode wherein the negative electrode comprises less than 100% of the carbonaceous particulate material according to the present disclosure as an active material. In other words, as one aspect of the present disclosure, negative electrodes comprising mixtures with other materials (graphite or other materials) are also contemplated.

  For example, in some embodiments, the carbonaceous particles may be natural graphite and / or synthetic graphite, and the negative electrode further comprises additional natural graphite, synthetic graphite and / or graphitized fine coke, preferably Additional natural graphite, synthetic graphite and / or graphitized fine carbon are present in small amounts, for example 2 to 10% by weight, or 3 to 5% by weight of the negative electrode.

  The disclosure also relates, in another aspect, to a lithium ion battery comprising a composition as defined herein as an active material on the negative electrode of the battery. Again, batteries wherein the negative electrode further comprises a mixture with other carbonaceous particulate materials are also included in this aspect of the present disclosure.

  An electric vehicle comprising a lithium ion battery, a hybrid electric vehicle or a plug-in hybrid electric vehicle, wherein the lithium ion battery comprises a lithium ion battery comprising the composition as defined herein in the negative electrode of the battery , A hybrid electric vehicle or a plug-in hybrid electric vehicle represents another aspect of the present disclosure.

  In yet another aspect, the present disclosure relates to an energy storage device comprising a hydrophilic surface modified carbonaceous particulate material according to the present disclosure.

  A further aspect of the present disclosure relates to a carbon brush or friction pad comprising a composition as defined herein.

  Furthermore, a further aspect of the present disclosure is a polymer, in addition to the polymer, comprising a composition as defined herein, typically in a proportion by weight of 5 to 95% by weight, preferably 10 to 85% by weight. It relates to a composite material.

  Furthermore, a ceramic, ceramic precursor material or green material comprising a composition as defined herein as a pore-forming material is a further aspect of the present disclosure.

Yet another aspect of the present disclosure is a dispersion comprising a liquid, preferably water or water based, and a composition as defined herein, wherein the dispersion is 40% by weight The aqueous dispersion containing the above-mentioned carbonaceous material has a viscosity as low as 2000 to 4000 mPa · s at a shear rate of 10 s ⁻¹ . Preferably, the viscosity at this concentration and shear rate is 2000 to 3000 mPa · s, or 2300 to 2600 mPa · s.

Other Applications A further aspect of the present disclosure is the use of a low springback carbonaceous particulate material having a springback of ≦ about 18% or ≦ about 15% as a carbonaceous additive and comprising the carbonaceous additive The use of the carbonaceous particulate material as a carbonaceous additive to increase cell capacity and / or cycle stability of Li-ion batteries while maintaining cell power density as compared to cells with no anode. In this context, “additive” means that the electrode is at least a substantial proportion of the active material of the negative electrode of the Li-ion battery (eg more than 30% by weight or more than 40% by weight or more than 50% by weight ) Is meant to include another carbonaceous material having a higher springback than the low springback carbonaceous particulate material.

  In this context, "maintaining" means that the power density of the cell does not decrease by more than 5%. In certain embodiments, the power density is not reduced by more than 3%, or more than 2%, as compared to a cell that does not include the carbonaceous additive. In this context, "increase" should be understood as an increase of at least 2%, at least 3%, at least 4%, or at least 5% of the respective cell parameter.

In some embodiments of this aspect, low spring back carbonaceous particulate material, any of the additional parameters as described above, such as at least 5 m 2 ^{/ g,} or at least 6 m 2 ^{/ g,} or at least 7m ² / It can be further characterized by the BET BET SSA of g and / or by being a highly crystalline graphite.

  Typically, the low springback carbonaceous particulate material is higher springback, eg, greater than 20% springback, which may be a surface modified carbonaceous material as defined herein. It is added as a minor component to the composition of the carbonaceous particles. In some embodiments, the low springback carbonaceous particulate material content added as a carbonaceous additive is less than 30%, or less than 20%, or 1 to 20% by weight of the composition. Or 2 to 15% by mass.

  The use of said low springback material makes it possible to produce a negative electrode which is a negative electrode and which carries a low loss per cycle to a Li-ion battery (cell) containing said electrode. In some embodiments, the loss per cycle of such a cell between the second and twelfth charge cycles is ≦ about 0.1%. In another embodiment, the reversible cell capacity of such a cell is 350 350 mAh / g.

  Another related aspect of the present disclosure is the use of the low springback carbonaceous particulate material as defined herein, as compared to a cell having an anode that does not contain the carbonaceous additive. Use of the low springback carbonaceous particulate material to increase electrode density appropriately for Li-ion batteries while maintaining cell power density.

  In this context, "maintaining" means that the power density of the cell does not decrease by more than 5%. In certain embodiments, the power density is not reduced by more than 3%, or more than 2%, as compared to a cell that does not include the carbonaceous additive.

In some embodiments of this aspect, low spring back carbonaceous particulate material, any of the additional parameters as described above, such as at least 5 m 2 ^{/ g,} or at least 6 m 2 ^{/ g,} or at least 7m ² / It is further characterized by the BET BET SSA of g and / or by being a highly crystalline graphite.

  Typically, the low springback carbonaceous particulate material in this aspect is a higher springback that may be a surface modified carbonaceous material as defined herein, eg, a spring of greater than 20% It is added as a minor component to the composition of carbonaceous particles having a bag. In some embodiments, the low springback carbonaceous particulate material content added as a carbonaceous additive is less than 30%, or less than 20%, or 1 to 20% by weight of the composition. Or 2 to 15% by mass.

  In certain embodiments, the resulting density of the electrode (using the same pressure) is increased by at least about 3%, 5%, 7% or 10% as compared to a cell having an anode without the carbonaceous additive It can be done.

  Suitable compositions for determining the various properties and parameters used to define the compositions and carbonaceous materials described herein are described in more detail below.

Methods of Measurement The percentage (%) values specified herein are by mass unless otherwise indicated.

Specific BET Surface Area, DFT Micropore and Mesopore Volume and Area This method is based on the reading of the absorption isotherm of liquid nitrogen at 77 K in the range of p / p 0 = 0.04 to 0.26. Nitrogen gas adsorption was performed with Quantachrome Autosorb-1. Monolayer volumes can be determined according to the procedure proposed by Brunauer, Emmet and Teller (Adsorption of Gases in Multimolecular Layers, J. Am. Chem. Soc., 1938, 60, 309-319). The specific surface area can be calculated based on the cross-sectional area of the nitrogen molecule, the monolayer volume and the mass of the sample. In order to evaluate the pore size distribution and the volume and area of micro and mesopores, isotherms determined at a pressure range of 0.01 to 1 at p / p0 of 77 K were processed by DFT calculation.
References: Ravikovitch, P., Vishnyakov, A., Russo, R., Neimark, A., Langmuir 16 (2000) 2311-2320; Jagiello, J., Thommes, M., Carbon 42 (2004) 1227-1232 .

Particle size distribution by laser diffraction The presence of particles in a coherent light beam causes diffraction. The dimensions of the diffraction pattern correlate with the particle size. A collimated beam from a low power laser lights up the cell containing the sample suspended in water. The beam leaving the cell is focused by optics. Next, the distribution of light energy at the focal plane of the system is analyzed. The electrical signal provided by the light detector is converted by the computer into a particle size distribution. This method results in the proportion of the total volume of particles to a discrete number of size classes forming a volumetric particle size distribution (PSD). This particle size distribution is typically defined by the D ₁₀ , D ₅₀ and D ₉₀ values, where 10 (volume)% of the particle population has a size smaller than the D ₁₀ value and 50 of the particle population % (Volume) has a size smaller than the D ₅₀ value, and 90 (volume)% of the particle population has a size smaller than the D ₉₀ value.

The particle size distribution data by laser diffraction cited herein were measured with a MALVERN Mastersizer S. To determine the PSD, a small amount of carbon material was mixed with a few drops of wetting agent and a small amount of water. The samples thus prepared were introduced into the storage container of the apparatus (MALVERN Mastersizer S) and subjected to ultrasonication for 5 minutes at a strength of 100% and a pump and stirring speed set to 40%, followed by measurements.
References: ISO 13320 (2009) / ISO 14887

Oxygen Content The mass fraction of oxygen in the solid sample was evaluated using the principle of inert gas melting or solid carrier gas thermal extraction. The sample was placed in a graphite crucible and inserted into an electrode furnace. A crucible was maintained between the upper and lower electrodes of the impulse furnace. After purging with an inert gas (He or Ar), a high current was passed through the crucible resulting in an increase in temperature (above 2500 ° C). The gas generated in the furnace was released into a flowing inert gas stream. The gas flow was then sent to the appropriate infrared (O as CO by NDIR) or thermal conductivity (N and H by TCD) detectors for measurement. Instrument calibration was performed using known reference materials.

Wettability / Surface Energy Measurement At 20 ° C., 1 cm ³ of graphite powder was spread on a microscope slide with a spatula and pressed at a pressure of 1 bar in order to produce as flat a surface as possible. An aqueous solution containing 2.7% by weight of 2-propanol was prepared with distilled deionized water. The surface tension of such solutions is 59 mN · m ⁻¹ or 59 mJ / m ² (extrapolated from Vazquez et al., J. Chem. Eng. Data, 1995, 40, 611-614). Thereafter, drops of this solution in a total volume of 10 μl were placed on the powder surface using an Easy Drop apparatus (Krijss GmbH, Hamburg, Germany).
Using Tangent method 1 and using System Shape Water (Strom et al., J. Colloid Interface Sci., 1987, 119, 352), using Drop Shape Analysis DSA1 software (Krijss GmbH, Hamburg, Germany) The contact angle between the solution droplet and the powder was determined. The material was considered to be hydrophilic if the contact angle in this test was less than 90 °. The material was considered to be hydrophobic if the contact angle exceeded 90 °.

pH value:
1 g of graphite powder was dispersed in 50 ml of distilled water containing 2 drops of imbentinTM and measured with a pH meter equipped with a calibrated pH electrode.

Fe content This analysis was carried out by means of an SDAR OES simultaneous emission spectrometer. The graphite powder ground to a maximum particle size of 80 μm by a vibratory mill was compressed into tablets. The sample was placed on an excitation stand under an argon atmosphere of the spectrometer. After that, fully automated analysis was started.

Ash Content Low-walled ceramic crucibles were heated at 800 ° C. in a muffle furnace and dried in a desiccator. A 10 g sample of dry powder (0.1 mg accuracy) was weighed into a low wall ceramic crucible. The powder was fired at a temperature of 815 ° C. to constant weight (at least 8 hours). The residue corresponds to the ash content. This is expressed as a percentage of the initial mass of the sample.
References: DIN 51903 and DIN 51701 (division method), ASTM C 561-91

Xylene density This analysis is based on the principle of liquid exclusion as defined in DIN 51 901. Approximately 2.5 g (0.1 mg accuracy) of the powder was weighed by a 25 ml picnometer. Xylene was added under vacuum (15 Torr). After several hours of residence time under standard pressure, the pycnometer was conditioned and weighed. This density represents the mass to volume ratio. This mass is given by the mass of the sample, and the volume is calculated from the difference in mass of the xylene filled pycnometer with and without the sample powder.
Reference: DIN 51 901

Scott density (Apparent density)
Scott density was determined by passing the dry carbon powder through a Scott volume meter according to ASTM B 329-98 (2003). The powder was collected in a 1 in 3 container (equivalent to 16.39 cm ³ ) and weighed to an accuracy of 0.1 mg. The mass to volume ratio corresponds to Scott density. The measurement was performed three times and the average value was calculated.

  The bulk density of the graphite was calculated from the mass of a 250 ml sample in a calibrated glass cylinder.

Tap density 100 g of dry graphite powder was carefully poured into a measuring cylinder. The cylinder was then fixed to a tapping machine based on an eccentric shaft and subjected to 1500 strokes. Volume readings were taken to calculate tap density.
Reference: DIN-ISO 787-11

Oil absorption number (carbon black)
Paraffin oil was added to the dried (1 hour at 125 ° C.) carbon black sample in the mixer chamber of the absorbance meter via a constant speed burette. As the sample absorbed the oil, the mixture changed from a free flowing state to a semiplastic aggregate state with an increase in viscosity. This increased viscosity is transmitted to the torque sensing system. When the viscosity reached a predetermined torque level, the absorptiometer and burette were shut off simultaneously. The amount of oil added was read from the burette. The volume of oil per unit mass of carbon black is the oil absorption.

Oil absorption value (graphite)
The slow filter paper was placed in a special centrifugally separated metal tube with an inner diameter of 13.5 mm and a sieve (18 mesh) at the bottom. In order to wet this filter, the tube is filled with 0.5 g paraffin oil (Marcol 82 from Exxon Mobile), and 521 g (1 g = 9.81 m / s ² , equivalent to 1500 rpm with a Sigma 6-10 centrifuge) Centrifuged for 30 minutes. After the wetting operation, the tube was weighed and 0.5 g of graphite powder was added. The graphite was covered with 1.5 g of paraffin oil and centrifuged at 521 g for 90 minutes. After centrifugation, the tubes were weighed. The oil absorption per 100 g of graphite powder was calculated based on the increase in amount.
-Internal method of Imerys

Raman Spectroscopy Raman analysis was performed using a LabRAM-ARAMIS Micro-Raman spectrophotometer from HORIBA Scientific, using a 632.8 nm HeNe laser. The ratio I _D / I _G is based on the ratio of intensities of so-called band D and band G. These peaks are respectively measured at 1350 cm ^-1 and 1580 cm ^-1, which is characteristic of the carbon material.
Crystallite size L _a
The crystallite size is the formula:
L _a [Angstrom] = C × (I _G / I _D )
Can be calculated from Raman measurements.
Here, the constant C has values of 44 Å and 58 Å for lasers having wavelengths of 514.5 nm and 632.8 nm, respectively. The intensities of the D and G band Raman absorption peaks are about 1350 cm ⁻¹ and 1580 m ⁻¹ respectively.

X-ray diffraction
XRD data were collected using a PANalytical X'Pert PRO diffractometer coupled with a PANalytical X'Celerator detector. The diffractometer has the following characteristics shown in Table 1.

  Data were analyzed using PANalytical X'Pert HighScore Plus software.

Interlayer spacing c / 2
The interlayer spacing c / 2 was measured by X-ray diffraction. [002] Interlayer spacing was calculated by determining the angular position of the peak maximum of the reflection profile and applying the Bragg equation (Klug and Alexander, X-ray diffraction Procedures, John Wiley & Sons Inc., New York, London (1967)). In order to avoid problems due to low absorption coefficient of carbon, instrument alignment and sample non-planarity, silicon powder which is internal standard is added to the sample and the peak position of graphite is recalculated with reference to the position of silicon peak did. Graphite samples were mixed with silicon standard powder by adding a mixture of polyglycol and ethanol. The resulting slurry was then applied on a glass plate with a blade at a spacing of 150 μm and allowed to dry.

Crystallite size L _c
The crystallite size was determined by analysis of the [002] diffraction profile and determining the half-width of the peak profile. Peak broadening should be influenced by crystallite size as suggested by Scherrer (P. Scherrer, Gottinger Nachrichten 2, 98 (1918)). However, this broadening is also influenced by other factors such as X-ray absorption, Lorentz polarization factors and atomic scattering factors. Several methods have been proposed to account for these effects by using an internal silicon standard and applying a correction function to the Scherrer equation. In the present disclosure, the method proposed by Iwashita (N. Iwashita, C. Rae Park, H. Fujimoto, M. Shiraishi and M. Inagaki, Carbon 42, 701-714 (2004)) was used. The preparation of the sample was the same as the determination of c / 2 above.

Springback Springback is a source of information on the resilience of compressed graphite powder. A predetermined amount of powder was packed into a 20 mm diameter die. After inserting the punch and sealing the die, air was exhausted from the die. The powder height was recorded applying a compressive force of 1.5 metric tons to produce a pressure of 0.477 t / cm ² . After releasing the pressure, this height was recorded again. Springback is the percentage (%) of the difference in height with respect to the height under pressure.

Adhesion Adhesion was measured according to the standard T-peel test specified in D1876 (ASTM International), which was adapted according to the following procedure: The active material mixture is the main graphite component and the minor graphite component over 1 hour with a shaker mixer Were prepared by combining in specific proportions. An aqueous slurry containing 97% active material, 1% CMC (carboxymethylcellulose) and 2% SBR (styrene-butadiene rubber) is prepared, cast at 160 μm on Cu foil, 15 minutes at 80 ° C. and 150 minutes Dried overnight at ° C. Rectangular specimens (3.5 cm × 7.14 cm) were cut from each sheet using a cutting die. Each specimen (25 cm ² ) was pressed at 400 kN for 1 second and then placed on the adhesive side of the clear tape. First, an elongated strip of non-adhesive paper (about 5 mm x> 3.5 cm) was placed parallel to the short side of the specimen. Transparent tape was cut along the edge of the test specimen. The non-adhesive paper allowed the two tabs to be folded in the opposite direction, resulting in a T-type adhesive specimen. The tab was attached to the grip and attached to a peel strength tester (LF Plus, Lloyd Instruments) equipped with a 20N load cell. T-peel testing was performed at a peel speed of 100 mm / min and a crosshead limit of 150 mm using Nexygen Plus software. The adhesion was calculated by subtracting the average value between 140 mm and 150 mm (the test pieces completely separated) from the average value between 20 mm and 100 mm. The resulting adhesion was divided by 0.035 m to convert the adhesion to T-peel strength (N / m).

Electrode Density The electrode density of the graphite electrode on a copper foil current collector (thickness 18 μm) having a loading of 7 to 8 mg / cm ² was measured. A disc-shaped test piece with a diameter of 12 mm was punched out and pressed at 20 MPa ( ² kN / cm ² ). After releasing the pressure, the electrode density was measured by measuring the electrode thickness with a height gauge (TESA-HITE) and calculating the density from the electrode block (without copper foil) and the electrode volume.

Electrochemical measurement:
Electrochemical Measurement A graphite slurry was prepared using graphite, CMC (carboxymethylcellulose) and SBR (styrene-butadiene rubber) in a mass ratio of 98: 1: 1 using a rotation-revolution mixer (THINKY, ARE-310). The slurry was applied onto a copper foil to prepare a graphite electrode adjusted to 7 to 8 mg / cm ² . All electrodes were pressed to 1.7 g / cm ³ .

Electrochemical measurements were made at 25 ° C. in a 2032 coin cell. The cell consists of a lithium electrode (diameter 14 mm, thickness 0.1 mm), polyethylene separator (diameter 16 mm, thickness 0.02 mm), 200 μL of electrolyte (EC: 1 M LiPF _{6 in} EMC 1: 3 v / v), and A graphite electrode (diameter 14 mm) was used and assembled in an Ar filled glove box.

  After assembly, measurements were made using a potentiostat / galvanostat (MACCOR, MODEL 4000). Charge the cell to 5mV at 0.1C (C rate of 0.1C means complete half cycle completed in 1 / 0.1 = 10 hours) then the current drops to 0.005C A potentiostatic step was performed until then and then discharged to 1.5 V at 0.1C. The capacity (specific charge) measured at the time of discharge was defined as a reversible capacity. The difference between the capacity measured during charging and the reversible capacity was defined as the irreversible capacity, and the Coulomb efficiency defined as a percentage was calculated by dividing the reversible capacity by the capacity measured during charging.

  After adjusting the SOC to 50%, each coin cell was opened, and the graphite electrode was reassembled into a new cell together with another graphite electrode that had been 50% SOC. The resulting symmetrical cell, whose voltage must be exactly 0 V, was connected to a potentiostat / galvanostat. The voltage after 20 seconds of discharge at 1 C divided by the current was defined as the electrode resistance.

  As a measure of cycle stability, the capacity loss per cycle of charge cycles 2 to 12 expressed as a percentage was calculated.

  High current rate performance, expressed as a percentage, was calculated from the ratio of reversible capacity measured at 2 C and 0.2 C discharge rates.

  Having described various aspects of the disclosure in general terms, it will be apparent to those skilled in the art that many modifications and slight variations are possible without departing from the spirit and scope of the present disclosure. .

Use Example Example 1
Several high springback surface modified graphite materials were made according to the general method outlined below. Table 2a summarizes the properties of these materials (particle size distribution, c / 2, L _c , L _a , ratio I _D / I _G , BET SSA and springback).

General Methods for Producing Surface-Modified Carbonaceous Particulate Materials The following is a general description of how the various carbonaceous materials shown in the Examples can be obtained.
Low springback component:
Synthetic Graphite:
Petroleum-based coke was graphitized at temperatures above 2500 ° C. under inert gas atmosphere and ground to a suitable particle size distribution.
Natural flake graphite:
Chemically or thermally refined natural flake graphite was ground to a suitable particle size distribution.
High springback component:
Method A:
Petroleum-based or coal-based coke was crushed and classified or sieved to adjust the desired particle size distribution, and then the fine coke was graphitized at temperatures above 2500 ° C. under an inert gas atmosphere. The obtained graphite is then subjected to air, carbon dioxide, water vapor or oxygen using a continuously operating or batch type rotary furnace, a rolling bed reactor, a fluidized bed reactor, a fixed bed reactor or a multistage hearth furnace. Oxidation was carried out at a temperature of 600 to 1000 ° C. or in ozone (at a lower temperature).
Method B:
Petroleum-based or coal-based coke was graphitized at temperatures exceeding 2500 ° C., and the obtained raw material graphite was crushed and shaped by mechanical processing so as to reach an appropriate particle size distribution. The finely divided graphite may then be hydrocarbon gas at a temperature of 600-1100 ° C. in a continuously operating or batch type rotary furnace, a rolling bed reactor, a fluidized bed reactor, a fixed bed reactor or a multistage hearth reactor. Alternatively, the surface was treated in a mixture of alcohol vapor and nitrogen. Gas flow rates, partial pressures, precursor gas types, residence times and feed rates were chosen to reach the desired BET SSA, as is well known to those skilled in the art.
Method C:
Chemically or thermally refined natural graphite was ground and shaped by mechanical processing to reach an appropriate particle size distribution. The finely divided graphite is then subjected to a hydrocarbon gas or alcohol at a temperature of 600 to 1100 ° C. in a continuously operating or batch type rotary furnace, rolling bed reactor, fluidized bed reactor, fixed bed reactor or multistage hearth furnace. The surface was treated in a mixture of steam and nitrogen. Gas flow rates, partial pressures, precursor gas types, residence times and feed rates were chosen to reach the desired BET SSA, as is well known to those skilled in the art.
Method D:
The graphite obtained by method B is air at a temperature of 500.degree. C. to 900.degree. C. in a continuously operating or batch type rotary furnace, rolling bed reactor, fluidized bed reactor, fixed bed reactor or multiple hearth furnace. Further treatment in an atmosphere of carbon dioxide, steam or oxygen.
Method E:
Graphite obtained by method C in a continuously operating or batch type rotary furnace, rolling bed reactor, fluidized bed reactor, fixed bed reactor or multistage hearth furnace, in an atmosphere of air, carbon dioxide, steam or oxygen At a temperature of 500.degree. C. to 900.degree.

  It should be noted that the oxidation treatment can conveniently be performed at lower temperatures or even at ambient temperature, especially when using ozone, which is a highly reactive gas.

The high springback surface modified graphite material is then combined with various amounts of several low springback graphite materials, based on which the properties are summarized in Table 2b (particle size distribution, c / 2, L _c , BET SSA, Scott density, oil absorption, springback and xylene density) are mixed for about 1 hour with a shaker mixer to obtain an active material mixture.

Thereafter, the active material mixture was treated with water to obtain an aqueous graphite slurry containing 97% of the above-mentioned specific active material. A graphite slurry was prepared using a rotation-revolution mixer (THINKY, ARE-310) at a mass ratio of 98: 1: 1 graphite, CMC (carboxymethylcellulose) and SBR (styrene-butadiene rubber). By applying the slurry onto a copper foil (thickness 18 [mu] m), the coating amount is to produce a graphite electrode that is controlled to ^{7mg / cm 2 ~8mg / cm 2} . Was pressed electrode density of 1.7 g / cm ^3.

Example 2
A negative electrode was prepared according to the procedure described in Example 1, mixing high springback graphite (graphite A) with low springback graphite as the main component. Specific percentages by weight of high springback graphite and low springback graphite used are shown in Table 3. The electrochemical measurements characterizing the resulting graphite negative electrode are also shown in Table 3.

Example 3
According to the procedure described in Example 1, another high springback graphite (graphite C) was mixed as a main component with low springback graphite to produce a graphite negative electrode. Specific percentages by weight of high springback graphite and low springback graphite used are shown in Table 4. The characteristics of the obtained graphite negative electrode are shown together in Table 4.

  As shown in Table 4, it was found that the low springback graphite material reduced the electrode resistance by a relatively small amount, but the higher amount resulted in an increase in resistance. In addition, increasing the amount of low springback graphite material resulted in a consistent increase in the reversible capacity of the electrode. This implies that there is a threshold where additional low springback graphitic materials begin to adversely affect battery performance. The current rate performance data for the compositions of Graphite C and Graphite 3 suggest that the performance is significantly degraded when the low springback graphite material exceeds about 15 wt% to 30 wt%.

Example 4
According to the procedure described in Example 1, a graphite negative electrode was manufactured by mixing high springback graphite with low springback graphite as a main component. The specific weight percentages of high springback graphite and low springback graphite used are shown in Table 5. The electrode parameters characterizing the obtained graphite negative electrode are also shown in Table 5.

Example 5
Following the procedure described in Example 1, a particular mixture of two high springback graphites was mixed with low springback graphites to produce a graphite negative electrode. The ratio of the high springback graphite mixture used to the particular springback low springback graphite component is shown in Table 6. The electrochemical measurements characterizing the resulting graphite negative electrode are also shown in Table 6.

Claims (42)

At least one surface modified carbonaceous particulate material; and at least one carbonaceous particulate material having lower springback than said at least one surface modified carbonaceous particulate material ("low springback carbon Quality material ");
A composition comprising: The surface-modified carbonaceous particulate material is a high springback surface-modified carbonaceous particulate material having a springback of 20% or more, or 30% or more, or 40% or more, and / or At least one low springback carbonaceous material particulate material has a springback of about 18% or less, or about 15% or less;
The composition of claim 1.   The composition according to claim 1 or 2, wherein the low springback carbonaceous material BET SSA is higher than the surface modified carbonaceous material BET SSA. The at least one surface modified carbonaceous particulate material is
i) ^{20 m} 2 / g, less than ^{15 m} 2 / g, or 1 to 10 m ² / g, or 1~8m ² / g, or 1~6m ² / g BET SSA of; or
^{ii) 4.1m 2 / g~20m 2 /} g, or 4.5m ² / g~15m ² / g, or 4.1m ² / g~10m ² / g of BET SSA,
The composition according to any one of claims 1 to 3, which comprises The composition according to any one of the preceding claims, wherein the surface-modified carbonaceous particulate material is characterized further by any of the following parameters, alone or in combination:
a. L _c / L _a ratio greater than 1.0, 1.5, 2.0, 2.5 or 3.0;
b. Crystallite size L _c (as measured by XRD) of 50-400 nm, or 60-200 nm, or 80-180 nm, or 100-150 nm;
c.5~100nm, 5~60nm, or (as measured by Raman spectroscopy) crystallite size _{L a} in 6～40Nm;
d. C / 2 distance of about 0.3353 to 0.3370 nm, or about 0.3354 to 0.3365 nm;
e. Oxygen content above 50 ppm, or above 90 ppm, or above 110 ppm;
f. A Fe content of less than 20 ppm, or less than 10 ppm, or less than 5 ppm; and / or g. Ash content less than 0.04%, or less than 0.01%, or less than 0.005%. The at least one surface modified carbonaceous particulate material is
h. A pH value of 5.0 to 7.0, or 5.0 to 6.5, or 5.2 to 6, or 5.3 to 5.5;
i. A xylene density of 2.24 to 2.26 g / cm ³ , or 2.245 to 2.255 g / cm ³ , or 2.25 to 2.255 g / cm ³ ; and / or j. An _ID / _IG ratio (R) of less than about 0.3, or less than about 0.25, or less than about 0.2, or less than about 0.15, as measured by a laser having an excitation wavelength of 632.8 nm. Showing (I _D / I _G ));
6. The composition of claim 5, further characterized by Wherein at least one surface-modified carbonaceous particulate material, the processing time of 2 to 30 minutes at a temperature of 500 to 1100 ° C., carbonaceous having a BET surface area of ^{1 m} 2 / g to about ^{15 m} 2 / g The composition according to claim 5 or 6, which is obtained by oxidation of a granular raw material.   6. A method according to any of the preceding claims, characterized in that said at least one surface-modified carbonaceous material comprises non-graphite, optionally amorphous, carbonaceous core particles with a carbon coating. The composition according to one item. The at least one surface modified carbonaceous particulate material is
k. A xylene density of 2.2 to 2.255 g / cm ³ , or 2.23 to 2.25 g / cm ³ ;
l. Crystallite size L _{c of} 80 to 350 nm;
m. Crystallite size L _{a of} 5 to 100 nm;
n. An I _D / I _G ratio (R (I _D / I _G )) greater than about 0.3, optionally about 0.4 to 1.0, as measured with a laser having an excitation wavelength of 632.8 nm. R ( _ID / _IG ); and / or o. Oxygen content above 80 ppm;
9. The composition of claim 8, further characterized by   Said non-graphite, optionally amorphous, carbon coating is treated with hydrocarbon gas at a temperature of 500-1200 ° C. for 3 to 120 minutes, if necessary, by chemical vapor deposition (CVD), if necessary The composition according to claim 8 or 9, obtained by chemical vapor deposition treatment in time. The non-graphite carbon coating of the at least one surface-modified carbonaceous particulate material is a hydrophilic non-graphite, optionally amorphous, carbon coating,
Optionally, the at least one hydrophilic surface-modified carbonaceous particulate material of the composition comprises
(I) a contact angle after 3 seconds of less than 90 °, less than 75 °, less than 70 °, or less than 65 °, and / or less than about 60 °, less than 40 °, less than 30 °, less than 25 °, or A contact angle after 5 seconds which is less than 20 °; and / or (ii) the surface of said hydrophilic surface-modified carbonaceous particulate material of at least 59 mJ / m ² or at least 62, 67 or 70 mJ / m ² energy,
The composition according to any one of claims 8 to 10, which exhibits a wettability characterized by   The composition of claim 11, wherein the carbon coating of the hydrophilic surface modified carbonaceous particulate material is comprised of oxidized amorphous carbon. The at least one hydrophilic surface-modified carbonaceous particulate material in the composition comprises
(I) an oxygen content of more than about 200 ppm, more than about 400 ppm, more than about 600 ppm, more than about 700 ppm, or more than about 800 ppm; and / or (ii) less than 10.0 m ² / g, 8.0 m ² Mesopore area less than 0.5 g / g, less than 5.0 m ² / g, less than 4.0 m ² / g, less than 3.8 m ² / g, or less than 3.6 m ² / g;
The composition according to claim 11 or 12, further characterized by The hydrophilic surface-modified carbonaceous particulate material is
(A) coating carbonaceous particles with non-graphite carbon, if necessary, by chemical vapor deposition (CVD), and (b) subjecting the carbonaceous particulate material obtained from step (a) to oxidation treatment, Increasing the hydrophilicity of the carbonaceous particulate material,
The composition according to any one of claims 11 to 13, obtained by The carbonaceous particles forming the core of the at least one surface-modified carbonaceous particulate material may be natural graphite, synthetic graphite, coke, hard carbon, graphitized fine coke, mixtures thereof, or even silicon Selected from the composition of such carbon particles comprising particles of tin, bismuth, antimony, aluminum, silver, SiO _x (x = 0.2 to 1.8) or SnO _x (including SnO and SnO ₂ ),
Optionally, the carbonaceous core particles are synthetic or natural graphite particles, or a mixture of synthetic or natural graphite particles and silicon particles,
The composition according to any one of claims 1-14. The at least one surface modified carbonaceous particulate material is
p. Particle size distribution (D ₉₀ ) of 10 to 50 μm, or 15 to 45 μm, or 20 to 40 μm;
q. Particle size distribution (D ₅₀ ) of 5-40 μm, or 7-30 μm, or 10-25 μm;
r. A tap density of greater than 0.7 g / cm ³ , or greater than 0.8 g / cm ³ , or greater than 0.9 g / cm ³ , or greater than 0.95 g / cm ³ , or greater than 1 g / cm ³ ;
s. An Fe content of less than 20 ppm, or less than 10 ppm, or less than 5 ppm; and / or t. Ash content less than 0.04%, or less than 0.01%, or less than 0.005%;
The composition according to any one of claims 1 to 15, further characterized by The low spring back carbonaceous particulate material is natural graphite, synthetic graphite, coke, exfoliated graphite, graphene, few-layer graphene, graphite fiber, nanographite, non-graphite carbon, carbon black, petroleum-based or coal-based coke, glassy carbon , Carbon nanotubes, fullerenes, carbon fibers, hard carbon, graphitized fine coke, or a mixture thereof, or further silicon, tin, bismuth, antimony, aluminum, silver, SiO _x (X = 0.2 to 1.8) Or selected from the composition of such carbon particles comprising SnO _x (containing SnO and SnO ₂ ) particles,
Optionally, the carbonaceous particles are synthetic or natural graphite particles, or a mixture of synthetic or natural graphite particles and silicon particles,
A composition according to any one of the preceding claims.   The composition according to any one of the preceding claims, wherein the at least one low springback carbonaceous material is not surface modified by an oxidized and / or non-graphitic carbon coating.   The at least one low springback carbonaceous material is highly crystalline graphite, and optionally, the graphite has a c of 0.3370 nm or less, 0.3365 nm or less, 0.3362 nm or less, or 0.3360 nm or less c. 19. A composition according to any one of the preceding claims, having a / 2 distance.   20. The composition of any one of the preceding claims, wherein the at least one low springback carbonaceous material is natural graphite or synthetic graphite. 21. The composition according to any one of the preceding claims, wherein said at least one low springback carbonaceous material, alone or in combination, is further characterized by any of the following parameters:
a. BET SSA greater than about 5 m ² / g, or greater than about 6 m ² / g, or greater than about 7 m ² / g;
b. Particle size distribution (D ₉₀ ) of 3 to 50 μm, or 5 to 30 μm, or 6 to 27 μm;
c. Particle size distribution (D ₅₀ ) of 1 to 30 μm, or 2 to 20 μm, or 3 to 15 μm;
d. Particle size distribution (D ₁₀ ) of 0.5 to 10 μm, or 1 to 7 μm, or 2 to 5 μm;
e. Crystallite size L _c (as measured by XRD) of 30 to 400 nm, or 50 to 350 nm, or 70 to 250 nm;
f. Scott density less than about 0.4 g / cm ³ , or less than 0.3 g / cm ³ , or less than 0.25 g / cm ³ ;
g. A xylene density of 2.24 to 2.27 g / cm ³ , or 2.25 to 2.265 g / cm ³ , 2.255 to 2.265 g / cm ³ ; and / or h. An _ID / _IG ratio (R) of less than about 0.3, or less than about 0.25, or less than about 0.2, or less than about 0.15, as measured by a laser having an excitation wavelength of 632.8 nm. Show (I _D / I _G )).   The content of the low springback carbonaceous material is less than about 30% by weight, or less than about 25% by weight, or less than about 20% by weight, or 1 to 25% by weight, or 2 to 25% by weight of the composition. 22. A composition according to claim 1 or 2 or 2 to 15 wt%, or 5 to 15 wt%, or 10 to 15 wt%.   The composition further contains at least one carbonaceous additive, and, if necessary, the content of the carbonaceous additive is 0% by mass to 10% by mass, or 0.5% by mass to 5% by mass The composition according to any one of the preceding claims, which is% or 1% to 4% by weight.   The carbonaceous additive is natural graphite, synthetic graphite, coke, exfoliated graphite, graphene, few-layer graphene, graphite fiber, nanographite, non-graphite carbon, hard carbon, graphitized fine coke, carbon black, petroleum-based or coal-based 24. The composition of claim 23, wherein the composition is selected from conductive additives such as coke, glassy carbon, carbon nanotubes, fullerenes, carbon fibers, or mixtures thereof.   The composition further comprises a polymer binder material, and if necessary, the polymer binder is styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), carboxymethyl cellulose (CMC), polyacrylic acid and its derivatives, 25. The composition according to any one of the preceding claims, selected from polyvinylidene fluoride (PVDF), or mixtures thereof.   26. The composition of claim 25, wherein the content of the polymeric binder is about 1% to about 5% by weight of the composition.   Said at least one surface modified carbonaceous particulate material is at least 2% higher, or at least 5% higher, or at least 10% higher than the springback of said at least one low springback carbonaceous particulate material; 27. A composition according to any one of the preceding claims, which has a springback which is at least 15% higher.   The at least one surface modified carbonaceous particulate material has about 25% to about 65% or about 55% to about 60% springback, and the at least one low springback carbonaceous particulate material 28. The composition according to any one of the preceding claims, wherein has a springback of about 5% to about 15% or about 7% to about 12%.   The composition comprises at least 75% by weight of the at least one surface modified carbonaceous particulate material and 2% by weight to 15% by weight of the at least one low springback carbonaceous particulate material. 29. A composition according to any one of the preceding claims.   The composition according to any one of the preceding claims, wherein the composition further comprises carbon black. Wherein at least one low springback carbonaceous particulate material _{D 90} diameter of 5 m to 30 m, has a _{D 50} diameter of 2 to 20 [mu] m, and a _{D 10} diameter of 1 to 7 [mu] m, claim 1-30 The composition according to one item.   32. Use of a composition according to any one of claims 1 to 31 in the manufacture of a negative electrode of a Li-ion battery, wherein said Li-ion battery is optionally an electric car, a hybrid electric car or an energy storage Use of the composition as used in a cell.   22. Use of the low springback carbonaceous particulate material according to any one of claims 1 or 17-21 as a carbonaceous additive, as compared to a cell having an anode free of said carbonaceous additive. 22. Low springback according to any one of claims 1 or 17-21 as a carbonaceous additive, which increases the cell capacity and / or cycle stability of a Li-ion battery while maintaining the power density of the cell. Use of carbonaceous granular material.   34. The use according to claim 33, wherein the loss per cycle between the second and the twelfth charging cycles is about 0.1% or less and the reversible cell capacity is about 350 mAh / g or more. 22. Use of the low springback carbonaceous particulate material according to any one of claims 1 or 17-21 as a carbonaceous additive, as compared to a cell having an anode free of said carbonaceous additive. , Increase the density of the Li-ion battery anode, while maintaining the cell's power density,
Optionally, the electrode density has been increased by at least about 3%, 5%, 7% or 10% as compared to a cell having an anode without said carbonaceous additive.
Use of said low springback carbonaceous particulate material.   An electrode comprising the composition according to any one of the preceding claims.   32. A Li-ion battery comprising the composition according to any one of claims 1 to 31 as active material in the anode of a Li-ion battery.   An electric vehicle, a hybrid electric vehicle, or an energy storage cell comprising the Li-ion battery according to claim 37.   32. A polymer composite material comprising the composition according to any one of claims 1 to 31, wherein the composition is present in a proportion of 5 to 95% by mass, preferably 10 to 85% by mass, as the case requires. To be a polymer composite material.   32. A carbon brush or friction pad comprising the composition according to any one of the preceding claims.   32. A ceramic, ceramic precursor material or green material comprising the composition according to any one of claims 1 to 31 as a pore forming material. A dispersion comprising a liquid, preferably water or water based, and a composition according to any of claims 1 to 31, wherein the dispersion comprises 40% by weight of said carbonaceous material In the aqueous dispersion containing the material, said dispersion having a low viscosity of 2000 to 4000 mPa · s at a shear rate of 10 s ⁻¹ .